掺杂稀土离子磷酸盐激光玻璃研究进展及其应用

由于国内外大型激光惯性约束聚变装置的兴建和光通信的迅速发展，磷酸盐激光玻璃，尤其是激光钕玻璃得到了前所未有的发展。本文介绍了目前国内外磷酸盐激光玻璃，主要是掺钕、掺铒、掺镱磷酸盐激光玻璃的最新研究进展及其应用。     

一种新的微型激光器材料--稀土掺杂玻璃

制得了具有双包层结构的掺Nd^3 和Yb^3 单模磷酸盐玻璃光纤,用中心波长为800nm的半导体激光器件钕光纤的光泵源,在室温下获得了波长为1．053um,输出功率为8．36mW的连续激光输出,用930nm的钛宝石激光泵浦掺镱光纤,也获得了1．067um的激光,研究了Nd^3 ,Yb^3 ,Er^3 离子掺杂四磷酸盐玻璃和氟化物玻璃的发光性能与浓度的关系,以及Yb^3 /Er^3 双掺杂玻璃的发光性能,得到了掺钕四磷酸盐玻璃,Yb^3 /Er^3 双掺四磷酸盐玻璃和掺氟铝酸盐玻璃等几种在微片激光器有应用前景的材料。     

磷酸盐玻璃中Tb^3＋离子的敏化发光与能量传递

研究了磷酸盐玻璃中Ｔｂ＾＋离子的敏化发光。结果表明；磷酸盐玻璃中Ｄｙ＾３＋，Ｃｅ＾３＋和Ｔｂ＾３＋产生敏化发光。确立了双掺Ｔｂ＾３＋和Ｄｙ＾３＋玻璃中Ｄｙ＾３＋－Ｔｂ＾３＋敏发化光的声子支助共振能量转移模型，双掺Ｔｂ＾３＋和Ｃｅ＾３＋玻璃中Ｃｅ＾３＋的激光发能通过无辐射能量共振转移每化发光，计算出Ｃｅ＾３＝－Ｔｂ＾３＋的有量传递效率，为确定最佳稀土离子掺加量提供了依据。     

N31型磷酸盐激光钕玻璃的耐水性

通过测试N31型掺钕磷酸盐激光玻璃在水浴中质量损失随时间的变化情况,讨论了该玻璃在水溶液介质中的化学稳定性和微观侵蚀机理.结果表明:N31型玻璃化学稳定性良好,在水溶液介质中各离子都有自身的溶解规律;经过一段线性溶解过程后,各离子的溶解速率明显下降,这是由于在钕玻璃局部表面生成了保护膜.     

磷酸盐激光玻璃除铂问题的研究

以我国激光核聚变所用的磷酸盐激光玻璃为对象,对铂进入玻璃的机制,熔炼条件对玻璃中铂含量的影响,熔炼条件与铂微粒形成的关系,以及对玻璃中形成的铂微粒的消除进行了研究.强氧化气氛、足够高的熔炼保温温度可以熔制不含铂微粒的磷酸盐激光玻璃.     

影响钾磷酸盐玻璃风化的因素

本文采用原子吸收分光光度计、激光椭圆偏光仪，红外反射谱，扫描电镜，Ｘ射线波长色散仪研究了温度、湿度和时间几个影响钾磷酸盐玻璃风化能力的因素，对钾磷酸盐玻璃风化的机理也进行了讨论。     

掺Y2O3磷酸盐隔热玻璃的制备及其性质的研究

以磷酸盐为主要原料,通过掺Y2O3制得了具有良好化学稳定性和可见光透过性的磷酸盐隔热玻璃.测定了玻璃的XRD、穆斯堡尔谱、IR光谱及可见-红外光谱,并对Y2O3改善磷酸盐玻璃的机制进行了合理的解释.     

掺铒高增益磷酸盐激光玻璃的研究进展

掺铒磷酸盐激光玻璃具有受激发射截面大、增益系数高和量子效率高等优点,目前已成为通信领域中广泛应用的一种新型光纤放大器材料.本文主要介绍其性能特点、最新研究进展和应用以及工艺改善方法.     

碱土金属氧化物对掺铒磷酸盐玻璃光谱性质的影响

以摩尔组成为72P2O5-8Al2O3-20RO(R=Mg,Ca,Sr,Ba)和(77-x)P2O5-8Al2O3-(15 x)BaO(x=0,5,10,15,20)掺铒磷酸盐玻璃系统为研究对象,测量和计算了掺铒磷酸盐玻璃的各种光谱参数,探讨了不同网络修饰体及其含量对掺铒磷酸盐玻璃光谱性质的影响。结果表明：玻璃折射率nd、积分吸收截面∑sbs发射截面σemi,J-O强度参量Ωt以及自发辐射几率AR都有较强的成分依赖性,主要决定于Er^3 离子周围结构和Er-O键共价性的变化;减小Er-O键的共价性可得到较高的∑abs,σemi以及AR。     

乳浊玻璃（四）

３．２磷酸盐乳浊玻璃为了防止氟化物的污染和利用磷灰石（ａｐａｔｉｔｅ）等天然矿物原料，在工业生产中已广泛应用磷酸盐乳浊玻璃。磷酸盐乳浊玻璃是在硅酸盐和硼硅酸盐玻璃基础成分中析出磷酸盐的晶粒而乳浊的。理想的磷酸盐晶体应为小球状分布，如图９所示。但如温度...     

Precipitation and Optical Properties of CsPbBr3 Quantum Dots in Phosphate Glasses

CsPbBr₃ quantum dots were precipitated in phosphate glasses through heat treatment. Controlled formation of CsPbBr₃ quantum dots was realized by adjustment of heat‐treatment conditions. Absorption and photoluminescence spectra of CsPbBr₃ quantum dots were tuned from 432 to 521 nm. Upon ultraviolet or blue light excitation, efficient photoluminescence from these CsPbBr₃ quantum dots doped phosphate glasses was observed.     

Tunable luminescence from bismuth‐doped phosphate laser glass by engineering photonic glass structure

Because of ultra‐broadband near‐infrared (NIR) emission bismuth‐activated glasses and fibers offer a new promising platform for novel photonic devices such as new type of optical amplifiers and broadly tunable fiber lasers. Yet, challenge remains to manipulate the NIR emission behavior of bismuth (Bi) in photonic glasses for efficient Bismuth‐doped fiber and fiber lasers. Here, by engineering phosphorus and aluminum's topology, broadly tunable NIR emission has been realized in Bismuth‐doped phosphate laser glass. Structural and optical analyses on ²⁷Al magic‐angle spinning nuclear magnetic resonance (MAS NMR), ³¹P MAS NMR, fourier transform infrared (FTIR) and static emission spectra suggest that polymerization of glass network can be improved by proper addition of aluminum into the system, which can be evidenced by partial conversion of Q² to Q³ species of phosphorus and the shift of P–O–P asymmetric stretching vibration toward lower frequency, and this turns out beneficial to Bi NIR emission. Embedding aluminum tetrahedra into phosphorus glass network can reduce the local crystal field around bismuth and therefore lead to the blueshift of Bi emission. This work presents new insights into the luminescent behavior of Bi ions in phosphate glass and it helps the design and fabrication of Bismuth‐doped glasses and fibers in future.     

掺稀土氟化物玻璃上转换发光材料发展概况

和传统的氧化物玻璃相比,氟化物玻璃具有声子能量低的特点,因此无辐射跃迁几率小,上转换量子效率高,使得掺稀土离子的氟化物玻璃具有高的发光效率.且稀土离子的能级在氟化物玻璃中具有较长的寿命,形成更多的介稳能级,有丰富的激光跃迁.利用稀土离子在氟化物光纤中的上转换特性,可以获得性能优良的光纤激光器.本文简述了掺稀土氟化物玻璃上转换激光材料的发光机理和研究进展.     

Photodarkening mechanisms of Pr3+ singly doped and Pr3+/Ce3+ co-doped silicate glasses and fibers

In this work, we revealed the possible mechanisms of the photodarkening in Pr³⁺ ions singly doped and Pr³⁺/Ce³⁺ co-doped silicate glasses and fibers induced by X-ray and 488-nm laser radiations and studied the role of Ce³⁺ in increasing radiation resistance in Pr³⁺-doped silicate glasses and fibers. The absorption, emission, electron paramagnetic resonance (EPR), radiation induced attenuation spectra, and X-ray photoelectron spectroscopy (XPS) of Pr³⁺ singly doped and Pr³⁺/Ce³⁺ co-doped silicate glasses before and after X-ray radiation were measured and analyzed. The fluorescence intensity and photoinduced attenuation of Pr³⁺ singly doped and Pr³⁺/Ce³⁺ co-doped silicate fibers at visible wavelengths pumped by 488-nm laser were measured and analyzed. The influence of Ce³⁺ ions co-doping on the spectroscopic properties of Pr³⁺ ions as well as the radiation-induced defects in silicate glasses was studied. Results demonstrate that both X-ray and 488-nm laser radiations will induce photodamage in Pr³⁺ ions-doped silicate glasses and fibers. Co-doping Ce³⁺ (by up to 1 mol%) is efficient to suppress the darkening induced by both X-ray and 488-nm laser radiations without influence on the luminescence behavior of Pr³⁺ ions in silicate glasses and fibers. Our studies demonstrate the promising potential of Pr³⁺/Ce³⁺ co-doped silicate glasses for visible lasing applications.     

Mechanism for broadening and enhancing Nd3+ emission in zinc aluminophosphate laser glass by addition of Bi2O3

Nd³⁺-doped phosphate laser glasses have been attracting much attention and widespread investigation due to their high solubility of rare earth (RE) ions, excellent spectroscopic properties, and large damage threshold. However, the narrow NIR emission bandwidth (less than 30 nm) of these Nd³⁺-doped phosphate glasses limits their further application toward ultrahigh power field and efficient fiber laser in new region. Here, we demonstrate the broadening and enhancing of Nd³⁺ NIR emission in laser glass of zinc aluminophosphate through tuning the glass structure and covalency of Nd-O bond without limiting the radiative properties of Nd³⁺. The maximum bandwidth of 1.05 μm emission is broadened to 50 nm, which is comparable to that of Nd³⁺-doped aluminate laser glasses. Simultaneously, the lifetime of ⁴F_3/2 level is elongated nearly by two times. Structural and optical properties of prepared glasses were discussed systematically to reveal the mechanism. Detailed analysis on optical spectra and glass structure indicates that the bandwidth is affected by not only the covalency of Nd-O but also the compactness of glass structure. Our results could enrich our understanding about the relationship between local glass structure and luminescence behaviors of active centers, and may be helpful in designing new RE-doped laser glass systems.     

不同氧磷比对磷酸盐包边玻璃性质的影响规律

包边技术是提高大尺寸激光玻璃饱和增益系数的关键技术.采用传统的方法熔制玻璃,研究了P2O5含量对P2O5-Al2O3-B2O3-CuCl-Na2O-ZnO磷酸盐包边玻璃的折射率、热膨胀系数、玻璃转变温度、膨胀软化温度以及化学稳定性的影响.结果表明:当P2O5的摩尔分数为60%左右,玻璃样品具有最高的折射率(1.5220)、最低的玻璃转变温度(352.4℃)、较好的化学稳定性[0.52mg/(cm2·d)]和适宜的热膨胀系数(128.427×10-7/℃),是用作钕磷酸盐激光玻璃硬包边的理想材料.     

Effect of BaF2 Content on Luminescence of Rare‐Earth Ions in Borate and Germanate Glasses

Rare‐earth‐doped oxyfluoride germanate and borate glasses were synthesized and next studied using spectroscopic methods. Influence of fluoride modifier on luminescence properties of rare earths in different glass hosts was examined. The excitation and emission spectra of Pr³⁺ and Er³⁺ ions in the studied glasses were registered. The emission spectra of Pr³⁺ ions in germanate and borate glasses are quite different and depend strongly on the glass host. In samples doped with Er³⁺ ions emission bands located around 1530 nm corresponding to the main ⁴I_13/2→⁴I_15/2 laser transition were registered, independently of the glass host. Quite long‐lived near‐infrared luminescence of Er³⁺ ions was observed for germanate glasses with low BaF₂ content, while in borate glass systems influence of barium fluoride on luminescence lifetimes is not so evident. The Judd–Ofelt calculations were used in order to determine quantum efficiencies of excited states of rare‐earth ions in germanate and borate glasses.     

PbO—Fe2O3-V2O5-P2O5玻璃结构与性能研究

钒、铁磷酸盐玻璃作为一种半导体材料受到许多研究者的关注。选择了PbO-V2O5-P2O5、PbO-Fe2O3-P2O5和PbO-Fe2O3-V2O5-P2O5三组玻璃系统,研究了V2O5和Fe2O3对磷酸盐玻璃结构和性能的影响。通过红外光谱(IR)和差热分析(DTA)发现,V2O5和Fe2O3对磷酸盐玻璃结构的影响不同,Fe2O3不但会降低[PO4]基团的桥氧数,还会打断P=O双键,以[FeO4]形式参加网络结构,使玻璃结构趋于稳定。